CN114902464A - Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same - Google Patents
Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same Download PDFInfo
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- CN114902464A CN114902464A CN202180007429.1A CN202180007429A CN114902464A CN 114902464 A CN114902464 A CN 114902464A CN 202180007429 A CN202180007429 A CN 202180007429A CN 114902464 A CN114902464 A CN 114902464A
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- formula
- electrolyte solution
- lithium secondary
- secondary battery
- aqueous electrolyte
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 96
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims description 58
- 230000000996 additive effect Effects 0.000 claims description 49
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
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- 125000000217 alkyl group Chemical group 0.000 claims description 26
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 10
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- 230000000052 comparative effect Effects 0.000 description 31
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- 239000008151 electrolyte solution Substances 0.000 description 25
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- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960002798 cetrimide Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011326 fired coke Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a non-aqueous electrolyte solution for a lithium secondary battery, comprising: a lithium salt; a non-aqueous solvent; a compound represented by chemical formula 1; and a compound represented by chemical formula 2; wherein the compound represented by chemical formula 1 and the compound represented by chemical formula 2 are contained at a volume ratio of 1:0.1 to 1: 1.5. In addition, the present invention provides a lithium secondary battery having improved high-temperature storage safety by containing the non-aqueous electrolyte solution for a lithium secondary battery.
Description
Technical Field
Cross Reference to Related Applications
The present application claims priority from korean patent application No. 10-2020-0127441, which was filed on 29/9/2020, the disclosure of which is incorporated herein by reference.
Technical Field
The present invention relates to a non-aqueous electrolyte solution for a lithium secondary battery containing an additive capable of improving flame retardancy, and a lithium secondary battery having improved high-temperature storage safety by containing the non-aqueous electrolyte solution.
Background
As personal IT devices and computer networks have been developed along with recent development of information society and the accompanying increase in dependence of the entire society on electric energy, there is a need to develop technologies for efficiently storing and utilizing electric energy.
In particular, as interest in solving environmental problems and realizing a sustainable-cycle society has arisen, research has been widely conducted on electric storage devices such as electric double layer capacitors and lithium secondary batteries typified by lithium ion batteries.
Among them, since lithium secondary batteries can be miniaturized to be suitable for personal IT devices, have high energy density and operating voltage, and have recently emerged as clean energy sources with low carbon dioxide emissions, lithium secondary batteries have been actively studied as power sources for energy storage, power sources for electric vehicles, and power sources for notebook computers and mobile phones.
A lithium secondary battery uses a material containing a lithium-containing transition metal oxide as a main component as a positive electrode, a lithium alloy or a carbonaceous material typified by graphite as a negative electrode, a separator is provided between the positive electrode and the negative electrode, and a nonaqueous electrolyte solution is used as a medium for lithium (Li) ion transfer. As the nonaqueous electrolyte solution, a nonaqueous electrolyte solution in which lithium hexafluorophosphate (LiPF) is to be used, for example, is widely used 6 ) The electrolyte is dissolved in one of organic solvents having a high dielectric constant (e.g., ethylene carbonate, dimethyl carbonate).
Most of organic solvents used in the non-aqueous electrolyte solution are volatile combustible substances, which are responsible for deterioration of safety of the battery under high-temperature storage because of the possibility of causing fire and explosion in the event of emergency of the battery.
Therefore, there is a need for a nonaqueous electrolyte solution composition that does not risk ignition and can improve the overall battery performance, such as high-rate charge and discharge characteristics, and safety when used in large-capacity batteries such as power sources for power storage or power sources for electric automobiles.
Disclosure of Invention
Technical problem
An aspect of the present invention provides a non-aqueous electrolyte solution for a lithium secondary battery, which has improved safety.
Another aspect of the present invention provides a lithium secondary battery in which high-temperature storage safety is improved by including the non-aqueous electrolyte solution for a lithium secondary battery.
Technical scheme
According to an aspect of the present invention, there is provided a non-aqueous electrolyte solution for a lithium secondary battery, including:
a lithium salt;
a non-aqueous solvent;
a compound represented by formula 1, and
a compound represented by the formula (2),
wherein the compound represented by formula 1 and the compound represented by formula 2 are contained at a volume ratio of 1:0.1 to 1: 1.5:
[ formula 1]
In the formula 1, the first and second groups,
R 1 to R 3 Each independently an alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine element.
[ formula 2]
In the formula 2, the first and second groups,
R 4 and R 5 Each independently hydrogen or alkyl having 1 to 5 carbon atoms,
R 6 to R 8 Each independently hydrogen, fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, and
R 9 is an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine.
According to another aspect of the present invention, there is provided a lithium secondary battery including the non-aqueous electrolyte solution for a lithium secondary battery.
Advantageous effects
The non-aqueous electrolyte solution of the present invention can improve the flash point of the electrolyte solution by including two types of compounds having a terminal group substituted with at least one fluorine element as an additive. As a result, ignition of the nonaqueous electrolyte solution at high temperature can be prevented or suppressed. Therefore, when the non-aqueous electrolyte solution is included, a lithium secondary battery having improved safety and battery characteristics during high-temperature storage may be realized.
Detailed Description
Hereinafter, the present invention will be described in more detail.
It should be understood that the words or terms used in the specification and claims should not be construed as meanings defined in common dictionaries, and it should be further understood that the words or terms should be interpreted as having meanings consistent with their meanings in the context of the related art and the technical idea of the present invention based on the principle that the inventor can appropriately define the meanings of the words or terms to best explain the invention.
Organic solvents used as a main component of a non-aqueous electrolyte solution in the manufacturing process of a lithium ion secondary battery are volatile combustible substances, in which they may reduce the safety of the battery during high-temperature storage because they may cause fire and explosion in the event of emergency of the battery.
Accordingly, the present invention is directed to a non-aqueous electrolyte solution for a secondary battery, which includes two additives capable of imparting flame retardancy to prevent or inhibit ignition of the electrolyte solution during high-temperature storage. In addition, the present invention is directed to providing a lithium secondary battery having improved safety and battery characteristics during high-temperature storage by including the non-aqueous electrolyte solution.
Nonaqueous electrolyte solution for lithium secondary battery
First, the nonaqueous electrolyte solution for a lithium secondary battery of the present invention will be explained.
The non-aqueous electrolyte solution for a lithium secondary battery of the present invention includes:
a lithium salt;
a non-aqueous solvent;
a compound represented by formula 1, and
a compound represented by the formula (2),
wherein the compound represented by formula 1 and the compound represented by formula 2 are contained at a volume ratio of 1:0.1 to 1: 1.5:
[ formula 1]
In the formula 1, the first and second groups,
R 1 to R 3 Each independently an alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine element.
[ formula 2]
In the formula 2, the first and second groups,
R 4 and R 5 Each independently hydrogen or alkyl having 1 to 5 carbon atoms,
R 6 to R 8 Each independently hydrogen, fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, and
R 9 is an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine.
(1) Lithium salt
Any lithium salt generally used in an electrolyte solution for a lithium secondary battery may be used as the lithium salt without limitation, and for example, the lithium salt may include Li + As a cation, and may include a cation selected from the group consisting of F - 、Cl - 、Br - 、I - 、NO 3 - 、N(CN) 2 - 、BF 4 - 、ClO 4 - 、B 10 Cl 10 - 、AlCl 4 - 、AlO 4 - 、PF 6 - 、CF 3 SO 3 - 、CH 3 CO 2 - 、CF 3 CO 2 - 、AsF 6 - 、SbF 6 - 、CH 3 SO 3 - 、(CF 3 CF 2 SO 2 ) 2 N - 、(CF 3 SO 2 ) 2 N - 、(FSO 2 ) 2 N - 、BF 2 C 2 O 4 - 、BC 4 O 8 - 、PF 4 C 2 O 4 - 、PF 2 C 4 O 8 - 、(CF 3 ) 2 PF 4 - 、(CF 3 ) 3 PF 3 - 、(CF 3 ) 4 PF 2 - 、(CF 3 ) 5 PF - 、(CF 3 ) 6 P - 、C 4 F 9 SO 3 - 、CF 3 CF 2 SO 3 - 、CF 3 CF 2 (CF 3 ) 2 CO - 、(CF 3 SO 2 ) 2 CH - 、CF 3 (CF 2 ) 7 SO 3 - And SCN - At least one of the group consisting of as an anion.
Specifically, the lithium salt may include one selected from the group consisting of LiCl, LiBr, LiI, LiBF 4 、LiClO 4 、LiB 10 Cl 10 、LiAlCl 4 、LiAlO 4 、LiPF 6 、LiCF 3 SO 3 、LiCH 3 CO 2 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiCH 3 SO 3 Lithium bis (fluorosulfonyl) imide (LiFSI: LiN (SO) 2 F) 2 ) Lithium bis (pentafluoroethanesulfonyl) imide (LiBETI: LiN (SO) 2 CF 2 CF 3 ) 2 ) And lithium bis (trifluoromethanesulfonyl) imide (LiTFSI: LiN (SO) 2 CF 3 ) 2 ) A single material of the group, or a mixture of two or more thereof. In addition to this, any lithium salt commonly used in an electrolyte solution of a lithium secondary battery may be used without limitation.
The lithium salt may be appropriately changed within a normal use range, but may be contained in the electrolyte solution at a concentration of 0.8M to 3.0M, for example, 1.0M to 3.0M, to obtain the best effect of forming a film for preventing corrosion of the electrode surface.
In the case where the concentration of the lithium salt satisfies the above range, the viscosity of the nonaqueous electrolyte solution may be controlled so that the optimal impregnation may be achieved, and the effect of improving the capacity characteristics and cycle characteristics of the lithium secondary battery may be obtained by increasing the mobility of lithium ions.
(2) Non-aqueous solvent
The non-aqueous solvent of the present invention may include a cyclic carbonate-based organic solvent, a linear carbonate-based organic solvent, or a mixed organic solvent thereof.
The cyclic carbonate-based organic solvent is an organic solvent that is a high-viscosity organic solvent and can well dissociate lithium salts in an electrolyte solution due to a high dielectric constant, wherein specific examples of the cyclic carbonate-based organic solvent may be at least one organic solvent selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), 1, 2-butylene carbonate, 2, 3-butylene carbonate, 1, 2-pentylene carbonate, 2, 3-pentylene carbonate, and vinylene carbonate, and wherein the cyclic carbonate-based organic solvent may include ethylene carbonate.
Further, the linear carbonate-based organic solvent is an organic solvent having a low viscosity and a low dielectric constant, wherein typical examples of the linear carbonate-based organic solvent may be at least one organic solvent selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate, and the linear carbonate-based organic solvent may specifically include ethylmethyl carbonate (EMC).
In order to ensure high ionic conductivity of the non-aqueous electrolyte solution of the present invention, the cyclic carbonate-based organic solvent and the linear carbonate-based organic solvent may be used by mixing in a volume ratio of 10:90 to 50:50, for example, 15:85 to 30: 70.
In addition, the non-aqueous solvent may further include at least one of a linear ester organic solvent and a cyclic ester organic solvent, which has a lower melting point and higher high temperature stability than the cyclic ester organic solvent and/or the linear carbonate organic solvent, thereby preparing an electrolyte solution having high ionic conductivity.
Specific examples of the linear ester-based organic solvent may be at least one organic solvent selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
Further, the cyclic ester-based organic solvent may include at least one organic solvent selected from the group consisting of γ -butyrolactone, γ -valerolactone, γ -caprolactone, σ -valerolactone and ε -caprolactone.
The non-aqueous solvent may be used without limitation by adding an organic solvent, which is generally used in an electrolyte solution for a lithium secondary battery, if necessary. For example, the non-aqueous solvent may further include at least one organic solvent selected from the group consisting of an ether-based organic solvent, an amide-based organic solvent, and a nitrile-based organic solvent.
(3) A compound represented by formula 1: first additive
In the present invention, in order to prevent ignition and explosion of the nonaqueous electrolyte solution during high-temperature storage and to prevent deterioration of the safety of the battery, a compound represented by the following formula 1 may be included as a first additive capable of imparting flame retardancy in the nonaqueous electrolyte solution.
[ formula 1]
In the formula 1, the first and second groups,
R 1 to R 3 Each independently an alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine element.
Since the compound represented by formula 1 includes a terminal group in a molecular structure in which at least one fluorine element is substituted, it has a high flash point, and thus, it may improve the flame retardancy of an electrolyte solution, and may form a strong Solid Electrolyte Interface (SEI) including a fluorine component on an electrode surface. In addition, since the compound represented by formula 1 includes an ether group in a molecular structure, it contributes to an increase in lithium solubility, and thus, it may reduce the viscosity of an electrolyte solution, while it may improve ion conductivity through interaction with lithium ions.
Therefore, since the non-aqueous electrolyte solution of the present invention includes the compound represented by formula 1 as the first additive, the viscosity and volatility are reduced and the flash point temperature is increased, so that ignition can be suppressed during high-temperature storage. Therefore, a lithium secondary battery having improved safety and battery characteristics during high-temperature storage can be obtained.
Specifically, in formula 1, R 1 To R 3 May each independently be an alkyl group having 1 to 4 carbon atoms substituted with at least one fluorine element, specifically, R 1 To R 3 May each independently be an alkyl group having 1 to 3 carbon atoms substituted with at least one fluorine element.
More specifically, the compound represented by formula 1 may be a compound represented by [ formula 1-1] below.
[ formula 1-1]
(2-trifluoromethyl-3-methoxyperfluoropentane (TMMP))
(4) A compound represented by formula 2: second additive
The non-aqueous electrolyte solution for a lithium secondary battery of the present invention may simultaneously include a compound represented by the following formula 2 as a second additive to further improve the flame retardant effect.
[ formula 2]
In the formula 2, the first and second groups,
R 4 and R 5 Each independently hydrogen or alkyl having 1 to 5 carbon atoms,
R 6 to R 8 Each independently hydrogen, fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, and
R 9 is an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine.
Since the compound represented by formula 2 includes a terminal group in a molecular structure in which at least one fluorine element is substituted, it has a high flash point, and thus, it may further improve the flame retardancy of an electrolyte solution, and at the same time, may form a strong SEI including a fluorine component on an electrode surface.
Accordingly, since the non-aqueous electrolyte solution of the present invention includes the compound represented by formula 2, the flash point temperature can be increased to suppress ignition during high-temperature storage, and thus, a lithium secondary battery having improved safety and battery characteristics during high-temperature storage can be realized.
Specifically, in formula 2, R 4 And R 5 Each independently hydrogen or alkyl having 1 to 3 carbon atoms, R 6 Is fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, R 7 And R 8 Each independently is hydrogen or fluorine, R 9 Is an alkyl group having 1 to 5 carbon atoms substituted with at least 1 fluorine.
Preferably, the compound represented by formula 2 may include at least one of the compounds represented by [ formula 2-1] and [ formula 2-2] below.
[ formula 2-1]
(2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane; TPTP)
[ formula 2-2]
(1H,1H, 5H-octafluoropentyl-1, 1,2, 2-tetrafluoroethyl ether (OTE))
Further, the volume ratio of the compound represented by formula 1 and the compound represented by formula 2 contained in the non-aqueous electrolyte solution of the present invention may be 1:0.1 to 1: 1.5.
If the compound represented by formula 2 is contained within the above range, high-temperature storage safety may be further improved since ignition may be prevented by improving the flame retardant characteristics of the battery and deterioration in performance may be minimized. That is, if the second additive is contained in a volume ratio of less than 0.1, the flame retardancy-improving effect may not be significant. In addition, if the second additive is included at a volume ratio of more than 1.5, battery performance may be deteriorated while the dissociation degree of the lithium salt is lower than that of a general electrolyte solution.
Specifically, the compound represented by formula 1 and the compound represented by formula 2 may be included at a volume ratio of 1:0.2 to 1:1.
The volume ratio of the non-aqueous organic solvent and the additive (i.e., the compound represented by formula 1 and the compound represented by formula 2) included in the non-aqueous electrolyte solution of the present invention may be 10:90 to 80:20, for example, 30:70 to 70: 30.
If the additive of the present invention, which includes the compound represented by formula 1 and the compound represented by formula 2, is included within the above range, high-temperature storage characteristics and battery characteristics can be further improved by improving the flame retardancy of the electrolyte solution.
If the total amount of the additives including the compound represented by formula 1 and the compound represented by formula 2 is greater than a volume ratio of 90, the flame retardant effect is significantly improved, but side reactions may increase so as to degrade battery performance, such as rate performance and cycle characteristics. Further, if the total amount of the additives including the compound represented by formula 1 and the compound represented by formula 2 is less than a volume ratio of 20, since it is difficult to continuously maintain the flame retardant effect, the effect of improving the flame retardancy and the battery characteristics may be reduced with the passage of time.
(5) Third additive
The non-aqueous electrolyte solution for a lithium secondary battery of the present invention may further include a third additive called a flame retardant to improve flame retardancy.
The third additive may include at least one compound selected from Succinonitrile (SN), trimethyl phosphate (TMP), and bis- (2,2, 2-trifluoroethyl) carbonate (DFDEC).
In this case, the compound represented by formula 1 and the third additive may be included in a volume ratio of 1:0.1 to 1:5, for example, 1:0.2 to 1: 1.5.
If the third additive is included within the above range, the flame retardancy of the electrolyte solution may be further improved. If the flame retarding effect may not be significant in the case where the amount of the third additive is less than 0.1 volume ratio, and if the amount of the third additive is more than 5 volume ratio, the resistance may increase with the increase in film thickness due to side reactions caused by the excess amount of the additive, and the battery performance may be deteriorated.
(6) Other additives
The non-aqueous electrolyte solution for a lithium secondary battery of the present invention may further include other additives, which may form a firm film on the surface of an electrode or may improve moisture-retaining ability by increasing dispersibility of the electrolyte solution, thereby further improving effects such as cycle characteristics and rate performance.
The other additives may include at least one compound selected from the group consisting of FEC, a nonionic surfactant, cetrimide (CTAC), cationic cetyltrimethylammonium bromide (CTAB), and anionic Sodium Dodecylbenzenesulfonate (SDBS).
The nonionic surfactant may include a compound represented by the following formula 3.
[ formula 3]
In the case of the formula 3, the reaction mixture,
r is hydrogen, acetyl, methyl or benzoyl, at least one of the two Rs is not hydrogen; m and n are each independently an integer from 2 to 20.
The content of the other additives may be less than 4 wt%, for example, 0.1 wt% to 3 wt%, based on the total weight of the non-aqueous electrolyte solution.
In the case where the amount of the other additive is less than 0.1% by weight, the effects of improving the low-temperature capacity and the high-temperature storage characteristics and the high-temperature lifespan characteristics of the battery are insignificant, and, in the case where the content of the other additive is greater than 4% by weight, side reactions in the electrolyte solution may excessively occur during the charge and discharge of the battery. In particular, if an excessive amount of the SEI-forming additives is added, the SEI-forming additives may not be sufficiently decomposed at high temperatures, so that they may be present in the form of unreacted or precipitated at room temperature in the electrolyte solution. Therefore, a side reaction may occur in which the battery life or the resistance characteristics are deteriorated.
Lithium secondary battery
Next, the present invention provides a lithium secondary battery comprising the above non-aqueous electrolyte solution for a lithium secondary battery.
The lithium secondary battery of the present invention may include a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and the non-aqueous electrolyte solution of the present invention.
Since the nonaqueous electrolyte solution of the present invention is explained above, the explanation thereof is omitted, and other components are explained below.
(1) Positive electrode
The positive electrode may be prepared by coating a positive electrode current collector with a positive electrode slurry including a positive electrode active material, a binder, a conductive agent, and a solvent, and then drying and rolling the coated positive electrode current collector.
The positive electrode collector is not particularly limited as long as it has conductivity without causing adverse chemical changes to the battery, and for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, or the like may be used.
In addition, the positive active material is a compound capable of reversibly intercalating and deintercalating lithium, wherein the positive active material may include a lithium transition metal oxide including lithium and at least one metal selected from cobalt, manganese, nickel or aluminum, and may specifically include a lithium manganese-based oxide (e.g., LiMnO) having high capacity characteristics and battery safety 2 、LiMn 2 O 4 Etc.) and lithium nickel manganese cobalt-based oxide represented by the following formula 4. Specifically, the positive electrode active material may include a lithium nickel manganese cobalt based oxide.
[ formula 4]
Li(Ni x Co y Mn z )O 2
(in formula 4, 0< x <1, 0< y <1, 0< z <1, and x + y + z ═ 1)
As a representative example, the positive active material may include Li (Ni) 1/3 Mn 1/3 Co 1/3 )O 2 、Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 、Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 、Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 And Li (Ni) 0.8 Mn 0.1 Co 0.1 )O 2 。
In particular, the positive electrode active material of the present invention preferably contains Li (Ni) 0.6 Mn 0.2 Co 0.2 )O 2 、Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 And Li (Ni) 0.8 Mn 0.1 Co 0.1 )O 2 Wherein the content of nickel in the transition metal is more than 60 atom percent. That is, since a higher capacity can be realized by increasing the amount of nickel in the transition metal, it is more advantageous to realize a higher capacity by using a transition metal having a nickel content of 60 atomic% or more. In the case where a transition metal oxide having a high nickel (Hi-Ni) content, in which the Ni content is greater than 0.55, is included as a positive electrode active material, the output characteristics of the lithium secondary battery can be improved by ensuring a high energy density.
For high Ni (Hi-Ni) oxide with Ni content greater than 0.55, due to Li +1 Ions and Ni +2 The size of ions is similar, and thus a cation mixing phenomenon occurs in which Li is present in a layered structure of a positive electrode active material during charge and discharge +1 Ions and Ni +2 The positions of the ions are interchanged. That is, when a nickel transition metal having a d orbital is coordinately bonded under an environment such as high temperature, it must have an octahedral structure according to the change in the oxidation number of Ni contained in the positive electrode active material, but the crystal structure of the positive electrode active material may be deformed and collapsed, and at the same time, a distorted octahedron is formed due to a non-uniform reaction of inversion of the order of energy levels or change in the oxidation number by external energy supply. In addition, another side reaction in which transition metals, particularly nickel metal, are eluted from the positive electrode active material may occur due to a side reaction of the positive electrode active material and the electrolyte solution when stored at high temperature, and thus, the overall performance of the secondary battery is deteriorated due to structural collapse of the positive electrode active material and depletion of the electrolyte solution.
Therefore, with the lithium secondary battery of the present invention, since the positive electrode comprising a high nickel (Hi-Ni) transition metal oxide as a positive electrode active material and the non-aqueous electrolyte solution comprising an additive having a specific configuration are used, a strong ion-conductive film is formed on the surface of the positive electrode, thereby suppressing Li +1 Ions and Ni +2 The cation mixing phenomenon of the ions effectively inhibits the side reaction between the positive electrode and the electrolyte solution and the metal dissolution phenomenon, so that the structural instability of the high-capacity electrode can be relieved. Therefore, the capacity of the lithium secondary battery can be ensuredAn amount of nickel transition metal sufficient so that the energy density can be increased to prevent a decrease in output characteristics.
The content of the positive electrode active material may be 80 to 99 wt%, for example, 90 to 99 wt%, based on the total weight of solid components in the positive electrode slurry. In this case, when the amount of the positive electrode active material is 80 wt% or less, the capacity may be reduced due to a reduction in energy density.
The binder is a component that contributes to adhesion between the active material and the conductive agent and adhesion to the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of solid components in the positive electrode slurry. Examples of binders may be fluororesin-based binders including polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE); rubber-based adhesives including Styrene Butadiene Rubber (SBR), acrylonitrile-butadiene rubber, or styrene-isoprene rubber; cellulose-based binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, or regenerated cellulose; polyol based binders including polyvinyl alcohol; polyolefin-based adhesives including polyethylene or polypropylene; a polyimide-based adhesive; a polyester-based adhesive; and a silane-based binder.
In addition, the conductive agent is a material that provides conductivity without causing adverse chemical changes in the battery, and the addition amount thereof may be 1 to 20% by weight based on the total weight of solid components in the positive electrode slurry.
As typical examples of the conductive agent, the following conductive materials can be used, for example: carbon powder such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder, such as natural graphite, artificial graphite or graphite having a well-developed crystal structure; conductive fibers, such as carbon fibers or metal fibers; conductive powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
In addition, the solvent may include: an organic solvent, such as N-methyl-2-pyrrolidone (NMP), and the amount thereof may be such that a desired viscosity is obtained when the positive electrode active material and optionally the binder and the conductive agent are included. For example, the solvent may be contained in an amount such that the concentration of the solid component in the slurry including the positive electrode active material and optionally the binder and the conductive agent is 10 to 60 wt%, for example, 20 to 50 wt%.
(2) Negative electrode
The anode may be prepared by coating an anode current collector with an anode slurry including an anode active material, a binder, a conductive agent, and a solvent, and then drying and rolling the coated anode current collector.
The negative electrode current collector generally has a thickness of 3 to 500 μm. The negative electrode collector is not particularly limited as long as it has high conductivity without causing adverse chemical changes in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, or copper or stainless steel surface-treated with one of carbon, nickel, titanium, or silver, or an aluminum-cadmium alloy, or the like may be used. Further, the negative electrode current collector may have fine surface roughness to improve the bonding strength with the negative electrode active material, similar to the positive electrode current collector, and the negative electrode current collector may be used in various shapes, such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven fabric body, and the like.
In addition, the anode active material may include at least one selected from the group consisting of lithium metal, a carbon material capable of reversibly intercalating/deintercalating lithium ions, a metal or an alloy of lithium with the metal, a metal composite oxide, a material that can dope and dedope lithium, and a transition metal oxide.
As the carbon material capable of reversibly intercalating/deintercalating lithium ions, a carbon-based anode active material generally used in a lithium ion secondary battery may be used without particular limitation, and as a typical example, crystalline carbon and/or amorphous carbon may be used. Examples of the crystalline carbon may be graphite such as irregular, planar, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon may be soft carbon (low-temperature sintered carbon) or hard carbon, mesophase pitch carbide, and fired coke, etc.
As the metal or the alloy of lithium with the metal, a metal selected from the group consisting of copper (Cu), nickel (Ni), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), silicon (Si), antimony (Sb), lead (Pb), indium (In), zinc (Zn), barium (Ba), radium (Ra), germanium (Ge), aluminum (Al), and tin (Sn), or an alloy of lithium with the metal may Be used.
As the metal composite oxide, one selected from the group consisting of PbO and PbO can be used 2 、Pb 2 O 3 、Pb 3 O 4 、Sb 2 O 3 、Sb 2 O 4 、Sb 2 O 5 、GeO、GeO 2 、Bi 2 O 3 、Bi 2 O 4 、Bi 2 O 5 、Li x Fe 2 O 3 (0≤x≤1)、Li x WO 2 (x is more than or equal to 0 and less than or equal to 1) and Sn x Me 1-x Me' y O z (Me: manganese (Mn), iron (Fe), Pb or Ge; Me': Al, boron (B), phosphorus (P), Si, the I, II th and III group elements of the periodic Table of the elements or halogen; 0<x is less than or equal to 1; y is more than or equal to 1 and less than or equal to 3; z is more than or equal to 1 and less than or equal to 8).
The material capable of doping and dedoping lithium may include Si, SiO x (0<x ≦ 2), Si-Y alloy (wherein Y is an element selected from the group consisting of alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, and combinations thereof, and is not Si), Sn, SnO 2 And Sn-Y (where Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, and is not Sn), SiO may also be used 2 And mixtures with at least one thereof. The element Y may be selected from the group consisting of Mg, Ca, Sr, Ba, Ra, scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf),
(Rf), vanadium (V), niobium (Nb), tantalum (Ta),
(Db), chromium (Cr), molybdenum (Mo), tungsten (W),
(Sg), technetium (Tc), rhenium (Re),
(Bh), Fe, Pb, ruthenium (Ru), osmium (Os),
(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), Cu, silver (Ag), gold (Au), Zn, cadmium (Cd), B, Al, gallium (Ga), Sn, In, Ge, P, arsenic (As), Sb, bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), polonium (Po), and combinations thereof.
The transition metal oxide may include lithium-containing titanium composite oxide (LTO), vanadium oxide, and lithium vanadium oxide.
The content of the negative active material may be 80 to 99% by weight, based on the total weight of solid components in the negative electrode slurry.
The binder is a component contributing to adhesion between the conductive agent, the active material, and the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of solid components in the anode slurry. Examples of binders may be fluororesin-based binders including polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE); rubber-based adhesives including Styrene Butadiene Rubber (SBR), acrylonitrile-butadiene rubber, or styrene-isoprene rubber; cellulose-based binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, or regenerated cellulose; polyol based binders including polyvinyl alcohol; polyolefin-based adhesives including polyethylene or polypropylene; a polyimide-based adhesive; a polyester-based adhesive; and a silane-based binder.
The conductive agent is a component for further improving the conductivity of the anode active material, wherein the conductive agent may be added in an amount of 1 to 20 wt% based on the total weight of solid components in the anode slurry. Any conductive agent may be used without particular limitation so long as it has conductivity without causing adverse chemical changes in the battery. For example, the following conductive materials may be used, for example: carbon powders such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black or thermal black; graphite powder such as natural graphite, artificial graphite or graphite having a well-developed crystal structure; conductive fibers such as carbon fibers and metal fibers; conductive powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
The binder and the conductive agent may be the same as or different from those of the positive electrode.
The solvent may include water or an organic solvent, such as NMP and alcohol, and may be used in such an amount that a desired viscosity is obtained when the anode active material and optionally the binder and the conductive agent are included. For example, the solvent may be contained in an amount such that the concentration of solid components in the anode slurry including the anode active material and optionally the binder and the conductive agent is 50 to 75 wt%, for example, 50 to 65 wt%.
(3) Diaphragm
Typical porous polymer films that are commonly used, for example, porous polymer films prepared from polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, may be used alone or laminated together as separators included in the lithium secondary battery of the present invention, and in addition, typical porous non-woven fabrics, for example, non-woven fabrics formed of high-melting glass fibers or polyethylene terephthalate fibers, may be used, but the present invention is not limited thereto.
The shape of the lithium secondary battery of the present invention is not particularly limited, but a cylindrical type, a prismatic type, a pouch type, or a coin type using a can may be used.
Hereinafter, the present invention will be described in more detail according to examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Examples
I. Preparation of non-aqueous electrolyte solution for lithium secondary battery
Example 1.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:0.25 and used as an additive.
Example 2.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-1 are mixed in a volume ratio of 1:0.25 and used as an additive.
Example 3.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 40:60 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1, the compound represented by formula 2-2, and Succinonitrile (SN) are mixed in a volume ratio of 1:0.25:0.25 and used as an additive.
Example 4.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:0.52 and used as an additive.
Example 5.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-1 are mixed in a volume ratio of 1:0.52 and used as an additive.
Example 6.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:1 and used as an additive.
Example 7.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-1 are mixed in a volume ratio of 1:1 and used as an additive.
Example 8.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:1.5 and used as an additive.
Comparative example 1.
The non-aqueous electrolyte solution is prepared by: mixing LiPF 6 Dissolving in a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 5:95Obtaining LiPF 6 The concentration of (3) was 1.2M.
Comparative example 2.
The non-aqueous electrolyte solution is prepared by: ethylene Carbonate (EC) and Succinonitrile (SN) were mixed at a volume ratio of 5:95, and LiPF was dissolved 6 So that LiPF 6 The concentration of (3) was 1.2M.
Comparative example 3.
The non-aqueous electrolyte solution is prepared by: to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 30:60, an additive (fluoroethylene carbonate (FEC)) was added at a volume ratio of 90:10, and LiPF was dissolved 6 So that LiPF 6 The concentration of (3) was 1.2M.
Comparative example 4.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (2) was 1.2M. In this case, the compound represented by formula 1-1 is used alone as an additive.
Comparative example 5.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (2) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:0.09 and used as an additive.
Comparative example 6.
The non-aqueous electrolyte solution is prepared by: adding an additive in a volume ratio of 50:50 to a non-aqueous solvent in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed in a volume ratio of 10:90, and dissolving LiPF 6 So that LiPF 6 The concentration of (3) was 1.2M. In this case, the compound represented by formula 1-1 and the compound represented by formula 2-2 are mixed in a volume ratio of 1:1.7 and used as an additive.
TABLE 1
In table 1, the abbreviations for the respective compounds have the following meanings.
SN: succinonitrile and its use
FEC: fluoroethylene carbonate
Preparation of lithium Secondary Battery
Example 9.
A positive electrode active material (Li (Ni)) 0.8 Mn 0.1 Co 0.1 )O 2 ) The conductive agent (carbon black) and the binder (polyvinylidene fluoride) were added to N-methyl-2-pyrrolidone (NMP) at a weight ratio of 97.5:1:1.5 to prepare a positive electrode slurry (solid content: 50 wt%). A 12 μm thick aluminum (Al) thin film as a positive electrode current collector was coated with the positive electrode slurry, dried and then rolled to prepare a positive electrode.
A negative electrode active material (graphite), a binder (SBR-CMC), and a conductive agent (carbon black) were added to water as a solvent at a weight ratio of 95:3.5:1.5 to prepare a negative electrode slurry (solid content: 60 wt%). A 6 μm thick copper (Cu) thin film as a negative electrode current collector was coated with the negative electrode slurry, dried and then rolled to prepare a negative electrode.
By stacking the positive electrodes in sequence, coated with inorganic particles (Al) 2 O 3 ) The polyolefin-based porous separator and the negative electrode to prepare an electrode assembly.
The electrode assembly was received in a pouch-type battery case, and the nonaqueous electrolyte solution for a lithium secondary battery of example 1 was injected thereinto to prepare a lithium secondary battery.
Example 10.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 2 instead of the non-aqueous electrolyte solution of example 1.
Example 11.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 3 instead of the non-aqueous electrolyte solution of example 1.
Example 12.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 4 instead of the non-aqueous electrolyte solution of example 1.
Example 13.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 5 instead of the non-aqueous electrolyte solution of example 1.
Example 14.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 6 instead of the non-aqueous electrolyte solution of example 1.
Example 15.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 7 instead of the non-aqueous electrolyte solution of example 1.
Example 16.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of example 8 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 7.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 1 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 8.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 2 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 9.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 3 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 10.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that a lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 4 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 11.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 5 instead of the non-aqueous electrolyte solution of example 1.
Comparative example 12.
A pouch type lithium secondary battery was prepared in the same manner as in example 9, except that the lithium secondary battery was prepared by injecting the non-aqueous electrolyte solution of comparative example 6 instead of the non-aqueous electrolyte solution of example 1.
Examples of the experiments
Experimental example 1 evaluation of flame retardancy
1g each of the nonaqueous electrolyte solutions of examples 1 to 8 and 1g each of the nonaqueous electrolyte solutions of comparative examples 1 to 6 were placed in a metal container, and the surface of the electrolyte solution was ignited with a gas lighter to check whether the electrolyte solution ignited, and the results thereof are shown in table 2 below.
In this case, the case where the electrolyte solution is ignited is represented by O, and the case where the electrolyte solution is not ignited is represented by x.
TABLE 2
| Whether there is fire or not | |
| Comparative example 1 | O |
| Comparative example 2 | × |
| Comparative example 3 | × |
| Comparative example 4 | × |
| Comparative example 5 | × |
| Comparative example 6 | × |
| Example 1 | × |
| Example 2 | × |
| Example 3 | × |
| Example 4 | × |
| Example 5 | × |
| Example 6 | × |
| Example 7 | × |
| Example 8 | × |
Referring to table 2, it can be confirmed that the non-aqueous electrolyte solutions of comparative examples 2 to 6 and the non-aqueous electrolyte solutions of examples 1 to 8, which contain a flame retardant additive, did not catch fire except for the electrolyte solution of comparative example 1, which does not contain an additive.
Experimental example 2 evaluation of cycle characteristics
After the lithium secondary batteries prepared in examples 9 to 16 and the lithium secondary batteries prepared in comparative examples 7 to 12 were subjected to an activation (formation) process at a rate of 0.2C, gas in each battery was removed through a degassing process.
An initial charge and discharge process was performed for 3 cycles using a charge/discharge device, in which each lithium secondary battery, from which gas was removed, was charged to 4.45V at a rate of 0.2C under constant current/constant voltage conditions at room temperature (25 ℃), was cut-off charged at 0.05C, and was discharged to 3.0V at a rate of 0.2C, as 1 cycle. In this case, a PNE-0506 charging/discharging device (manufacturer: PNE SOLUTION) is used as the charging/discharging device for charging and discharging the battery.
Subsequently, 74-cycle charging and discharging processes were performed using a charging/discharging device, in which each lithium secondary battery was charged to 4.45V at a rate of 1.0C under constant current/constant voltage conditions at a high temperature (45 ℃), charged with 0.05C cutoff, and discharged to 3.0V cutoff at a constant current of 1.0C rate, as 1 cycle.
Subsequently, the discharge capacity after 74 cycles was measured, and cycle characteristics were obtained by comparing the discharge capacity after 74 cycles with the initial capacity, and the results thereof are shown in table 3 below.
Experimental example 3 evaluation of Rate Properties
After the formation process was performed by charging the lithium secondary batteries prepared in examples 9 to 16 and the lithium secondary batteries prepared in comparative examples 7 to 12 to a state of charge (SOC) of 100% at a rate of 0.2C, a degassing process was performed after aging for 4 hours. Each of the degassed lithium secondary batteries was charged to 4.2V at a rate of 0.5C at 25 ℃, initially charged under constant current-constant voltage (CC-CV) conditions at a current of 0.05C, and discharged to 3.0V at a rate of 0.5C under CC conditions, and the initial discharge capacity value was checked.
Then, after each lithium secondary battery was charged at 25 ℃ at a rate of 0.5C to 4.2V, charged at a current of 0.05C under a constant current-constant voltage (CC-CV) condition, and discharged at a rate of 2C and a rate of 4C to 3.0V, respectively, discharge capacities at 2C and 4C with respect to an initial discharge capacity were evaluated and shown in table 3 below.
TABLE 3
Referring to table 3, the secondary batteries of examples 9 to 16 had discharge capacity retention rates of about 93% or more after 74 cycles, wherein it can be understood that the discharge capacity retention rates after 74 cycles were improved as compared to the secondary batteries of comparative examples 7 to 12.
Further, referring to table 3, the secondary batteries of examples 9 to 16 had a rate performance at 2C of 97.5% or more and a rate performance at 4C of 90.0% or more, wherein it can be understood that the rate performance at 2C and the rate performance at 4C were improved as compared with the secondary batteries of comparative examples 7 to 12, respectively.
Claims (10)
1. A non-aqueous electrolyte solution for a lithium secondary battery, comprising:
a lithium salt;
a non-aqueous solvent;
a compound represented by formula 1; and
a compound represented by the formula (2),
wherein the compound represented by formula 1 and the compound represented by formula 2 are contained at a volume ratio of 1:0.1 to 1: 1.5:
[ formula 1]
Wherein, in the formula 1,
R 1 to R 3 Each independently an alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine element;
[ formula 2]
Wherein, in the formula 2,
R 4 and R 5 Each independently hydrogen or alkyl having 1 to 5 carbon atoms,
R 6 to R 8 Each independently hydrogen, fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, and
R 9 is an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine.
2. The non-aqueous electrolyte solution for lithium secondary batteries according to claim 1, wherein, in formula 1, R 1 To R 3 Each independently an alkyl group having 1 to 4 carbon atoms substituted with at least one fluorine element.
3. The non-aqueous electrolyte solution for lithium secondary batteries according to claim 1, wherein, in formula 1, R 1 To R 3 Each independently an alkyl group having 1 to 3 carbon atoms substituted with at least one fluorine element.
4. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the compound represented by formula 1 is a compound represented by formula 1-1:
[ formula 1-1]
5. The non-aqueous electrolyte solution for lithium secondary batteries according to claim 1, wherein, in formula 2, R 4 And R 5 Each independently hydrogen or alkyl having 1 to 3 carbon atoms, R 6 Is fluorine or an alkyl group having 1 to 7 carbon atoms substituted with at least one fluorine, R 7 And R 8 Each independently is hydrogen or fluorine, and R 9 Is an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine.
6. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the compound represented by formula 2 includes at least one of compounds represented by formulae 2-1 and 2-2:
[ formula 2-1]
[ formula 2-2]
7. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the compound represented by formula 1 and the compound represented by formula 2 are contained at a volume ratio of 1:0.2 to 1:1.
8. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, further comprising at least one additive selected from succinonitrile, trimethyl phosphate, and bis- (2,2, 2-trifluoroethyl) carbonate.
9. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 8, wherein the compound represented by formula 1 and the additive are contained at a volume ratio of 1:0.1 to 1: 5.
10. A lithium secondary battery comprising the non-aqueous electrolyte solution for a lithium secondary battery according to claim 1.
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| PCT/KR2021/013287 WO2022071734A1 (en) | 2020-09-29 | 2021-09-29 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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| JP2010123287A (en) * | 2008-11-17 | 2010-06-03 | Panasonic Corp | Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| WO2019039763A1 (en) | 2017-08-22 | 2019-02-28 | 리켐주식회사 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| DE102018000713A1 (en) * | 2018-01-30 | 2018-07-12 | Daimler Ag | Electrolytic composition for a rechargeable, electrochemical energy storage cell and rechargeable, electrochemical energy storage cell with the electrolyte composition |
| KR102237375B1 (en) | 2018-04-03 | 2021-04-06 | 삼성에스디아이 주식회사 | Electrolyte of rechargeable lithium battery and rechargeable lithium battery including same |
| CN111740160B (en) * | 2018-09-21 | 2022-04-15 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| CN110061293B (en) * | 2019-05-23 | 2021-09-03 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using the same |
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